Polymers stabilized with trimethylol propane phosphites

ABSTRACT

WHERE N IS AT LEAST 1, R is H or alkyl, R1 is aryl, alkyl, haloaryl, haloalkyl, alkaryl, alkenyl and haloalkenyl, R2 is a hydrogenated dihydric phenol moiety, R3 is H or R1, and Q   AND TRIADS AND POLYMERS OF TRIADS OF THE FORMULA   Phosphites, useful for stabilizing polymers, are provided of the formulae

[ POLYMERS STABILIZED WITH TRIMETI-IYLOL PROPANE PHOSPHITES [75]Inventor: Ali'in Guttag, Bethesda, Md.

[73] Assignee: Weston Chemical Corporation, New

York, N.Y.

[22] Filed: Jan. 16, I970 [2]] Appl. No.: 3,501

Related US. Application Data [63] Continuation-impart of Scr. No758,701, Sept. l0,

I968, abandoned.

[52] US. Cl 260/458 R, 260/2 P, 260/318 R, 60/477?! 260/880 R, 260/837i26 260/899 [51] Int. Cl. C08f 45/58 1 [58] Field of Search 260/2 P, 47P, 45.8 R, 260/4595 .R, 897 R, 899, 927, 937, 45.95 L

[56] References Cited UNITED STATES PATENTS 1,932,889 l0/l933 Groff260/23 2,934,507 4/l960 Chadwick et al. 260/23 3,341,629 9/1967 Larrison260/928 3,516,963 6/1970 Friedman 260/458 Primary Examiner-Donald E.Czaja Assistant Examiner-R. A. White Attorney, Agent, or Firm-Cushman,Darby & Cushman [111 3,819,571 June 25, 1974 [57] I ABSTRACT Phosphites,useful for stabilizing polymers, are provided'of the formulae I L 00 IIR! and triads and polymers of triads of the formula 0 mort where n is atleast 1, R is H or alkyl, R is aryl, alkyl, haloaryl, haloalkyl,alkaryl, alkenyl and haloalkenyl, R is a hydrogenated dihydricphenolmoiety, R is H or R and Q is v OCH: R

13 Claims, No Drawings POLYMERS STABILIZED WITH TRIMETHYLOL PROPANEPHOSPHITES This patent application is a continuation-in-part of patentapplication, Ser. No. 758,701, filed September 10, I968, which has beenabandoned.

The present invention relates to novel phosphites.

It is an object of the present invention to prepare novel phosphites.

Another object is to develop novel stabilizers for bydrocarbon polymers,halogen-containing polymers, natural and synthetic rubbers and otherpolymers.

A more specific object is to prepare stabilizers for rigid polyvinylchloride resins.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has now been found that these objects can be attained by preparingphosphites having the formula R-C P-OR; or 3-0 POB1 H2011 HzOR't isreacted with a hydrogenated dihydric phenol of the formula where R and Rare as above and R is a hydrogenated dihydric'phenol moiety. For eachrepeating unit above 1, one less mole of the compound offormula (3) isused than the number of moles of formula (2a) or (2b), when no end groupreaction is desired. One additional mole of the compound of formula (3)is required for each end group to be reacted. The reaction proceeds withthe splitting out of either water and/or the corresponding alcohol, ROl-l for each. repeating unit. The number of moles of R OH split outwill increase by 2 for each additional repeating unit above l. Ofcourse, the use of an appropriate number of additional moles of thehydrogenated dihydric phenol will be required to also providehydrogenated dihydric phenol end groups.

The compounds of formula (2a) may be prepared by reacting on amole-to-mole basis a trimethanol alkyl of the formula CH OH R- C-CHa- 0H CHz-QH where R, may be the same or different and as above and stoppingthe reaction when two moles of the cone sponding alcohol or phenol, R,OHare split offl Alternately, the mono ethers of the trimethanol alkyls offonnula (4) may be prepared and reacted with the compounds of formula(5) to provide the starting material of formula (2b) to make novelmonomers. The ethers may be made, for example, by reacting one mole ofthe compound of formula (4) with 1 mole of an alcohol of the formula ROl-l, where R, is as above, in the presence of an acid catalyst, e. g.sulfuric acid, and splitting out 1 mole of water.

The phosphite of formula (lb) may be prepared by reacting the compoundof formula (2a) on a mole-tomole basis, with the phosphites of formula(5 and with splitting off one mole of R OH to form the compounds of theformula:

Or alternately a chlorophosphite may be reacted instead of the compoundsof formula (5). e.g.

pound of formula (3) is required for each end group.

Again the number of moles of R' Ol-l split out were increased by 2 foreach additional repeatingv unit above 1'. The splitting, out of R' -OH.is preferably continued until a molecular weight of the product of aboutat least 1000 is obtained, e.g. 1000 to 30,000 preferably 1500 to 4000such as 3000. Of course, the mole bases of the reaction may be varieddepending upon the end groups desired. While formula (la) and (lb) areshown with end groups, those formulae are intended to also include, bydefinition, the same compounds but without any end groups or with atleast one end group reacted.

and RR, and R are as above. This corresponds to formula (lb) where n is2 and each end group has been reacted. However, when additional moles of(3) and (6) are used. reactions between units across the other OR, groupwill occur and the triads of the formula or haloaryl, with the alkylsubstituent as described above, i.e. up to 20 carbon atoms, and againthe halo atom or atoms being suitably a mono or disubstituted haloaryl,e.g. benzyl, napthyl, phenyl, p-methyl phenyl, o-methyl phenyl, ethylphenyl, m-propyl phenyl, hexyl phenyl, p-nonyl phenyl, dodecyl phenyl,p-octadecyl phenyl, etc., and the alkaryl being suitably a mono ordisubstituted with halo as described above. R, also can be alkenyl, e.g.allyl, crotyl or oleyl.

10 For example, the l,3,2-dioxaphosphorinanes may be Z-ethoxy-S ethyl(S-hydroxymethyl-l,3,2-dioxaphosphorinane). TheS-hydroxymethyl-l,3,2-dioxaphosphorinane nucleus is designated as A andmay-also be 2-ethoxy-5 methyl A, 2-ethoxy-5-propyl A, 2-ethoxy-5- Ehexyl A, 2-ethoxy-5-decyl A, 2-ethoxy-5-dodecyl A, j

2-ethoxy-5-octadecyl A, 2-ethoxy-5-chloromethyl A, 2-ethoxy-5-bromoethylA, 2-ethoxy-5-chlorohexyl A, 2-ethoxy-5-idooctyl A, and the samecompounds as above but instead of the Z-ethoxy substituteddioxaphosphorinanesthe 2 position may be substituted with,

tylphenoxy, bromododecylphenoxy, such compounds 1 for example, apropoxy, decoxy, octadecoxy, oleyloxy, chloroethoxy, chloropropoxy,bromodecoxy, and

iodohexoxy, phenoxy, chloro or bromo phenoxy, ethylphenoxy,hexylphenoxy, dodecylphenoxy, chloropen- 0C: CC:

or the position isomers thereof are produced when the number of moles ofR OH per repeating unit are split out according to the following table.

R,OH out (moles) Triads n Total Per :i

l 4 4 2 9 4.5 3 14 4.67 4 l) 4.75 5 24 4.80 6 29 4.83 7 34 4.85 8 394.86 9 44 4.88 10 49 4.89 l l 54 4.9] II! 59 4.)! I7 84 4.94

chloroethyl, l-chloropropyl, chlorodecyl, chlorododecyl, bromohexadecyland idooctadecyl, etc. Suitably the haloalkyl is a mono or disubstitutedhaloalkyl and the halogen substituent is chlorine, bromine or iodine.The position of the halo substituent is not important and may be in anyposition. Also R, may be a ry], alkaryl including Z-phenoxy-S-ethyl A,2-p-nonylphenoxy-5- ethyl A, 2-oleyloxy-5-ethyl A,2-octadecyloxy-5-ethyl A, and the same compounds as above but the 5-hydroxymethyl group may instead be the methoxy ether thereof with thesame substituents named above in the 2 position. Such compounds, ofcourse. are produced from the reaction of the trimethanol 'alkyls offormula (4) which may be for instance trimethanol ethane, trimethanolpropane, trimethanol hexane, trimethanol heptane, trimethanol dodecaneand trimethanol hexadecane, and the triphosphites of formula (5) whichmay be for instance trimethyl phosphite, triethyl phosphite, tributylphosphite, trihexyl phosphite, tridodecyl phosphite, tri (chloroethyl)phosphite, tri (chlorohexyl) phosphite, tri (bromodecyl) phosphite,triphenyl phosphite, tri (ethylphenyl) phosphite, tri (butylphenyl)phosphite, tri (p-dodecylphenyl) phosphite, tri (p-octadecylphenyl)phosphite, tri (chloropentyl phenyl) phosphite, tri (chlorodecyl phenyl)phosphite, tri (bromooctadecyl phenyl) phosphite, methyl-diethylphosphite, tri (p-nonylphenyl)-phosphite, ethyl-dimethyl phosphite,methyl-dihexyl phosphite, methyl-dioctadecyl phosphite, ethyl-di(chloroethyl) phosphite, ethyl-di (chlorododecyl) phosphite, ethyl-di(bromohexadecyl) phosphite, hexyl dioctadecyl phosphite, decyl-dibutylphosphite, methyl-diphenyl phosphite, ethyl-di phenyl phosphite,hexyl-di phenyl phosphite, octadecyldiphenyl phosphite, diphenyl oleylphosphite, (diphenyl A 9-octadecenyl phosphite), diethyl oleylphosphite, diphenyl stearyl 5 phosphite (diphenyl octadecyl phosphite),dibutyl stearyl phosphite, diphenyl hexadecyl phosphite, di-ocresylstearyl phosphite, triallyl phosphite tricrotyl phosphite, dimethyllinoleyl phosphite, dimethyl stearyl phosphite, dimethyl oleylphosphite, dimethyl tetradecyl phosphite, dimethyl lauryl phosphite,dimethyl alpha naphthyl phosphite, diphenyl beta naphthyl phosphite,diphenyl p-nonylphenyl phosphite, diphenyl ooctadecylphenyl phosphite,diphenyl m-octadecenyl phosphite (diphenyl oleyl phosphite), diphenyl4-tbutylphenyl phosphite, diphenyl 2,4-dichlorophenyl phosphite,diphenyl p-cyclohexylphenyl phosphite, triallyl phosphite, diphenyl2,4-di(nonyl) phenyl phosphite, dimethyl 2, 4 d i 2,4- dibutyl) phenylphosphite,

stituents for R, of formula (2b) or (6) or by choosing specificsubstituents for R, of formula (20) various position isomers of theproducts can be obtained.- For example, when the R substituent on themethoxy group of (2b) is a lower alkyl e.g. ethyl and the R substituentof phosphite moeity of formula (2b) is a higher alkyl or aryl, e.g.phenyl, the alcohol split out between the R, of the methoxy group andthe OH group of the hydrogenated dihydric phenolwill split out at alower temperature (due to a lower-boiling point of the resultingalcohol) than will the phenol split out between'the R of the phosphitemoeity and the OH group of the hydrogenated dihydric phenol. Thus theproduct formed would have the repeating units OCH: R R CHaO P-O 2ETOH CCHzO tris 2,4-xylenyl phosphite, tris 2,6-xylenyl phosphite.

Compounds such as dimethyl stearyl phoshite can be i conveniently formedfor example by heating 1 mole of trimethyl phosphite with 1 mole ofstearyl alcohol, e.g. in the presence of a small amount of sodiummethylate and removing 1 mole of methyl alcohol. Compounds such asdiphenyl p-nonylphenyl phosphite can be formed in analogous fashion byheating 1 mole of triphenyl phosphite with 1 mole of p-nonylphenol andremoving 1 mole of phenol per se.

As used in the present specification and claims, the term hydrogenateddihydric phenol signifies that all of the armatic double bonds have beencompletely hydrogenated. Examples of hydrogenated dihydric phenols usedto form the products of the present invention are 4,4'-isopropylidenedicylcohexanol (also called his (4- hydroxycyclohexyl) dimethyl methaneor hydrogenated Bisphenol A), di (4-hydroxycyclohexyl) methane, di(4-hydroxycyclohexyl), bis (2- hydroxycyclohexyl) dimethyl methane,1,4-dihydroxycyclohexane, di (4-hydroxy-3-methylcyclohexyl)- dimethylmethane, di (4-hydroxy-3-meth'ylcyclohexyl) methyl methane, di(4-hydroxy-3-methyl cyclohexyl) cyclohexyl methane, di(4-hydroxycyclohexyl) sulfone, di (4-hydroxycyclohexyl) sulfide, di (3-hydroxycyclohexyl) dimethyl methane, 4,4'-methylene bis(2-methyl-6-t-butylcyclohexanol), di (4- hydroxycyclohexyl) ether,l,3-dihydroxycyclohexane, di (3-chloro-4-hydroxycyclohexyl) dimethylmethane.

The preferred starting hydrogenated dihydric phenols are'bisphenol, themost preferred being hydrogenated Bisphenol A.

The l,3,2-dioxaphosphorinanes of formula (2a), (2b) may be prepared bythe reaction of the trimethanol alkyls of formula (4) with thetriphosphites of formula (5) at room temperature or lower or at above.room temperature, e.g. to 100C. and at atmospheric, superatmospheric orsubatmospheric pressure, e.g. 5 mm. of Hg to 100 atmospheres.Preferably, however, the reaction is carried out under a vacuum of about14mm. of Hg or less and at a temperature suffiditions may be used, andalso the vacuum and temperatures noted above are also preferred in orderto more 'easily remove the alcohol or water split out. ltshgulilsqQEBQEQIMIbXEbQPSgfiiifaent subreacted at a lower temperature before asecond molecule of HOR --OH reacted with a phenyl group at reacted at alower temperature before the second molecule of HOR OH reacted with aphenyl group on the ends of the molecule. Further, when R, is the same,a

mixture of position isomers will result. The same situation is, ofcourse, true for the product of formula lb) as well as the triads offormula (7).

Under the circumstances, by choosing the specific substituents for R,,one may produce nearly pure products of only one of various positionisomers or a mixture thereof as described. As is quite apparent, theparticular substituents for R are chosen according to the boiling pointof the alcohol (or phenol) split out at the pressure being used duringthe reaction. In order to be concise in this specification and to notrepeat details known to the art, additional details of such reactionswill be apparent from the disclosures of US. Pat. Nos. 3,341,629;3,293,327; and 3,053,878, which disclosures are hereby incorporated byreference.

. The reactions set forth above are all preferably catalyzed with 0.1 to5% based on the weight of the phosphite reactant or reactants of acatalyst'which usually is a secondary phosphite, e.g. a dialky]phosphite, a diaryl phosphite or a dihaloaryl phosphite or an alkalinecatalyst. Examples of suitable catalysts are diphenyl phosphite, di(Z-methylphenyl) phosphite, di (4- dodecylphenyl) phosphite, di(4-octadecyl-phenyl) phosphite, di (2-chlorophenyl) phosphite, di(2,4-dimethylphenyl) phosphite, di (4-bromophenyl) phosphite, diethylphosphite, dicyclohexyl phosphite, phenyl 3-methylphenyl phosphite,dioctadecyl phosphite, dimethyl phosphite, sodium phenolate, sodiumdecylate, potassium p-cresylate, sodium ethylate, sodium octadeconolate,sodium hydride, sodium metal, potassium metal, lithium methylate, sodiumcetylate,

trimethyl benzyl ammonium hydroxide and other qua- The compounds of thepresent invention are useful as heat and light stabilizers and asantioxidants. They apbilized with the phosphites of the presentinvention include chlorinated polyethylene having about 14 to about 75%,e.g. 26% chlorine, polyvinyl chloride, polyvinylidene chloride,polyvinyl bromide, polyvinyl fluoride, polyvinylidene fluoride,polytetrafluoroethylene, copolymers of vinylidene chloride andacrylonitrile (e.g. 80:20) or vinyl chloride (e.g. 85:15), copolymers ofvinyl chloride with 1 to 90%, preferably 1 to 40%, by weight ofcopolymerizable materials such as vinyl acetate, vinylidene chloride,vinylidene fluoride, diethyl fumarate, diethyl maleate and other alkylfumarates and maleates, vinyl propionate, methyl acrylate, ethylacrylate, butyl acrylate, 2-ethylhexyl acrylate and other alkylacrylates, methyl methaerylate, butyl methacrylate and othermethacrylates, methyl alpha chloroacrylate, styrene, vinyl ethyl ether,vinyl methyl ketone, acrylonitrile, allylidene diacetate,trichloroethylene, etc. Typical copolymers include vinyl chloridevinylacetate (96:4), vinyl chloride-vinyl acetate (87:13), vinylchloride-vinyl acetate-maleie anhydride (8621311), vinylchloride-vinylidene chloride (95:5), vinyl chloride-diethyl fumarate(95:5), vinyl 'chloridetrichloroethylene (95:5), vinylchloride-acrylonitrile (60:40), vinyl chloride-2-ethylhexyl acrylate(80:20). They can also be used to stabilize resins where thehalogen-containing component is present in minor amount, e.g.acrylonitrilevinyl chloride copolymer (85: 15) or halogenated rubberse.g. polychloroprene, chlorinated polyisobutylene, chlorinated naturalrubber, chlorine containing polyurethanes, etc.

As is conventional in the art when the novel phosphites are employedwith halogen-containing resins, there can be added barium, cadmium andzinc salts and synergistic activity is noted in this connection. Thus,there can be included 0.5 to 10% of salts such as mixed barium-cadmiumlaurates, barium laurate, cadmium laurate, zinc stearate, cadmium2-ethyl hexoate, barium nonylphenolate, barium octylphenolate, bariumstearate, zinc octoate.

There can also be incorporated in the vinyl chloride resins and the like0.5 to 10% of organot'in compounds, particularly sulfur-containingcompounds such as dibutyltin bis (octylthioglycollate).

Conventional phenolic antioxidants can also be incorporated in an amountof 0.1 to l0%, e.g. 2,2- methylene bis (4-methyl-6-t-butylphenol),2,4,6,-tri-tbutylphenol, 4,4-isopropylidenephenol, etc.

The novel phosphites of the present invention can also be incorporatedin an amount of 0.01 to as stabilizers for hydrocarbon polymersincluding monoolefin polymers such as polyethylene, polypropylene,ethylene-propylene copolymers, (e.g. 80:20, 50:50, 20:80),ethylene-propylene terpolymers, e.g. ethylenepropylcne-cyclooctadieneterpolymer, ethylenebutene-l copolymer, ethylene-decenel copolymer,

polystyrene, polyolefin, e.g. diolefin polymers such as natural rubber,rubbery butadiene styrene copolymer (:25, 60:40), cis isoprene polymer,polybutadiene, polyisobutylene, isobutylene-butadiene copolymer (butylrubber, e.g. 97:3, 98511.5). There can also be stabilized ABS rubbersand resins (acrylonitrilebutadiene-styrene terpolymers, e.g. 50:40:10).

They can be used in an amount of 0.01 to 20% to stabilize polyurethanes,(e.g. from toluene diisocyanate and polypropylene glycol molecularweight 2025), polyesters, e.g. Dacron (polyethylene terephthalate),polymeric tetramethylene terephthalesiophthalatesebacate, or unsaturatedpolyesters, e.g. ethylene glycol propylene glycol adipate-maleatemolecular weight 5000 and the corresponding polymer modified with 10%styrene, nylon, e.g. polyhexamethylene adipamide, Delrin (polymerizedoxymethylene) and Celcon (oxymethylene copolymer), polyvinyl butyral,polysulfones from conjugated diolefins, sulfur dioxide and amono-ethylenically unsaturated compound, e.g. a terpolymer of butadiene,sulfur dioxide and styrene as set forth in Example 1 of Mostert U.S.Pat. No. 3,377,324, polycarbonates e.g. the reaction product ofBisphenol A with phosgene or diphenyl carbonate as well as otherpolycarbonates set forth in Fritz U.S. Pat. No.

When incorporated in hydrocarbon polymers it is frequently advantageousto add conventional phenolic antioxidants as set forth above andconventional additives such as dilauryl thiodipropionate.

They are also useful as stabilizers for foods, oils, lubricants, andother products which deteriorate on oxidation.

The compounds of the invention are also useful as flame and fireproofing additives in polyurethane, hydrocarbon polymers, celluloseesters and ethers, e.g. cellulose acetate, methyl cellulose, ethylcellulose, cell s?asstatsrpr piqua@1919-...

The fieldof greatest utility at the moment, however, appears to be asstabilizers for rigid vinyl chloride resins. Since the compounds of thepresent invention maybe monomeric with readily defined structures, it issurprising that they will act as stabilizers for rigid vinyl chlorideresins since the only phosphites previously found to satisfactorilystabilize rigid polyvinyl chloride are polymeric phosphites. The rigidpolyvinyl chloride resins normally do not contain over 10% plastacizer 19 29 .bss maletaxslsxe fl fplastisi 'sr The invention will beillustrated by the following examples, but it is to be understood thatthe invention is not limited thereto but is fully applicable to thebreadth of the foregoing disclosure. In the examples all percentages andparts are by weight unless otherwise stated.

EXAMPLE 1 grams (1 mole) of trimethanol propane were heated to about 110C. with 310 grams (1 mole) of triphenyl phosphite and with 3 grams ofdiphenyl phosphite and subjected to vacuum distillation at 8 to 10 mm.until 188 grams (2 moles) of phenol were removed leaving aclear liquidin the pot. The reaction mixture was cooled by blowing nitrogen throughthe pot and then fractionated. The Z-phenoxy, S-ethyl, 5-hydroxymethyl-l,3,2-di-oxaphosphorinane was recovered. The product hadthe formula EXAMPLE 2 514 grams (2 moles) of the 2-phenoxy, S-ethyl,hydroxymethyl l,3,2-dioxaphosphorinane of Example 1 and 480 grams (2moles) of hydrogenated bis-phenol A were heated at increasingtemperatures in the presence of 5 grams of diphenyl phosphite as acatalyst while being subjected to vacuum distillation at 5 to mm. untilabout 2 moles of phenol and 1 mole of water were distilled off. Theresidue in the pot was about 7 l 4 grams of viscous liquid producttogether with the diphenyl phosphite catalyst. The catalyst was removedby vacuum fractionation to yield the purified product of the formula ofla) where R is R is -Ch CH and R is H and n is 2.

EXAMPLE 3 The procedure of Example 1 was repeated replacing thetrimethanol propane with trimethanol decane and the corresponding5-nonyl dioxaphosphorinane was recovered.

EXAMPLE 4 The 5-nonyl dioxaphosphorinane of Example 3 was used in theprocedure of Example 2 to replace the 5- ethyl dioxaphosphorinane andproduced the product of Example 2 except that R is octyl.

EXAMPLES The procedure of Example 2 was repeated replacing the S-ethyldioxaphosphorinane with the 5- chloropropyl dioxaphosphorinane andproduced the product of Example 2 except that R is chloropropyl.

EXAMPLE 6 The procedure of Example I was repeated except the trimethanolpropane and triphenyl phosphite was re placed with the followingreactants:

The reaction products of Example 6, ipe. (A), (B), (C) and (D) wereserially reacted with the hydrogenated bisphenol A according to theprocedure of Example 2. All of the products obtained were viscousliquids.

EXAMPLE 8 257 grams (l mole) of Z-phenoxy, 5-ethyl-5 hydroxymethyll',3,2-dioxaphosphorinane was heated at increasing temperatures with 310grams (1 mole) of triphenyl phosphite and 3 grams of diphenyl phosphiteunder a vacuum of 5 to 10 mm. until 94 grams l mole) of phenol wereremoved. The reaction mixture was then cooled and vacuum fractionated torecover purifled the 2-phenoxy-5-(diphenyl phosphite methoxy)-5 ethyl,l,3,2-dioxaphosphorinane product of the formula EXAMPLE 9 950 grams (2moles) of the product of Example 8 were heated at increasingtemperatures with 600 grams (25 moles) of hydrogenated bis-phenol Aunder8 to 12 mm. vacuum and with 6 grams of diphenyl phosphite untilapproximatelyv grams (approximately 2.5 moles) of phenol were distilledoff. The cooled product was a glassy solid and had the formula of lb)where R is R, is phenyl, R is -CH2CH3 and n is 4.

EXAMPLE 10 phite methoxy)-5 ethyl, 1,3,2-dioxaphosphorinane, and

2 -phenoxy-5 (dichlorodecyl phosphite methoxy)-5 ethyl, l,3,2-dioxaphosphorinane.

EXAMPLE 1 1 Each of the products of Example 10 was serially reacted withbis-phenol A and the corresponding products were obtained. Each productobtained was a glassy highly viscous semi-solid.

EXAMPLE I 2 2 moles of 2-phenoxy-5-(diphenyl phosphite methoxy)-5 ethyl,l,3,2-dioxaphosphorinane was heated with 3.2 moles of hydrogenatedbis-phenol A under a vac- 3 ,8 1 9,5 7 l 1 1 12 v uum of 8 to 12 mm. andwith 8 grams of diphenyl phosphosphite methoxy)-5-ethyl,l,3,2-dioxaphosphorinane phite until 4 moles of phenol was distilled off.The with 3.2 moles of hydrogenated bisphenol A. The prodproduct had theformula uct is a glassy solid having pendant stearyl groups.

CH3 cm 011,011: 0H HO E -O-P \('JCHQOII"OY(BO OCH; cmom OH; P/\(IJ-CHQO--II O@A}@OH 09?? m. 31 w.

and was a glassy solid. 7 EXAMPLE 17 i The procedure'of Example 12 isrepeated except that 2 moles of 2-phenoxy-5-(phenyl,isodecyl phosphitemethoxy)-5-ethyl, l ,3,2-dioxaphosphorinane is used with 3.2 moles ofhydrogenated bisphenol A. The product is a glassy solid.

EXAMPLE 1;

The procedure of Example 12 was repeated but using 8 moles of thephosphorinane and 12.8 moles of the hydrogenated bis-phenol A andsplitting out 19 moles of phenol. The product had the formula EXAMPLE 181 part of the product of Example 12, 2 parts of barium-cadmium laurateand 100 parts of rigid polyvinyl chloride were ground and mixed togetherwith heating. The mixed resin showed good stabilization.

R1 v EXAMPLE 19 g I 1 part of the product of Example 13,-together with 2=O Q O P ORZO"QO POROH parts of calcium stearate were milled into 100parts of RzO 4 v polyvinyl chloride and 50 parts of dioctyl phthalate tow W give a stabilized product. where R2 was 40 EXAMPLE 20 CH @J 3 1 partof the product of Example 14 was heated on v a a mill and milled into100 parts of polyvinyl chloride, v parts of dioctyl phthalate and 2parts of calcium stearate to give a stabilized product.

R, was phenyl,

--- EXAMPLE 21 CHZCHZ- The procedure of Example 12 is repeated exceptthat -P CH2, 2 moles of 2-phenoxy-5-(phenyl,oleyl phosphite me- 0c{,' 7thoxy)-5-ethyl, 1,3,2-dioxaphosphorinane is used with n was 7 50 3.2moles of hydrogenated bisphenol A. The product is a glassy solid havingpendant oleyl groups.

EXAMPLE 14 As will be appreciated, the hydrogenated dihydric procedureof Example 13 was repeated with 20 phenol residue of the presentphosphites may have the formula moles of the phosphorinane and 32 molesof hydroge- R R nated bisphenol A with 49 moles of phenol being split1!) out. i on The product was a hard glassy solid with the formula Wwhere R or alkyl, X is O, S, S0 or as ta nalelsyeat w 8- EXAMPLE 15 Theprocedure of Example 12 was repeated except R, that there is used 2moles of 2-phenoxy-5-(phenyl,pnonyl phenyl phosphite methoxy)-5 ethyl,1,3,2-dioxa- E phosphorinane with 3.2 moles of hydrogenated bisphenol A.The product is a glassy solid having pendant pwhere R2 and R3 arehydrogen lower alkyl or phenyl:

19 lpheny groups and n is Zero or one.

EXAMPLE 16 As noted above, the mole ratios of the reactants may Theprocedure of Example 12 was repeated except vary depending upon the endgroups reacted. Hence, there ie used '2 mnles nf 2-nhennxv-5-(nhenvl.stearvl' with re ard to formula la) if 1 mole of formula (2b) 13 isreacted with 1 mole of formula (3) the product will be:

cm R

However, if 2 moles of (2b) are reacted with 1 mole of (3) the productwill be OCH: R

with no end group reacted. The results will be similar in the reactionto produce the products of formula lb) or (7). Likewise, if 2 moles of(2b) are reacted with 2 moles of (3) one end group will be CH OR OH orif 3 moles of (3) are reacted each end group will be likewise terminatedby OH. Hence all of these combinations are included, by presentdefinition in the formulae of the products, noted above.

Also, as can be appreciated, the number of moles of R OH split out willdepend on the number of repeating units and the number of end groupsreacted. For example, when formula (6) is reacted with formula (3) andno end group reaction is desired. the moles will be as and the positionisomers thereof and where R is hydrogen or alkyl, R is aryl, alkyl,haloaryl, haloalkyl, alkaryl, alkenyl and haloalkenyl, R is ahydrogenated dihy- 10 dric phenol moiety, R is H or R and n is aninteger of at least 1.

2. A composition according to claim 1 where n of formula (2) is equal to2.

3. A composition according to claim 1 wherein the polymer is a vinylchloride resin.

polymer is a monoolefm polymer.

6. A composition according to claim 5 wherein the polymer ispolypropylene.

7. A composition according to claim 1 wherein the polymer is selectedfrom the group consisting of diolefin homopolymers, butadiene-styrenecopolymer and acrylonitrile-butadiene-styrene terpolymer.

8. A composition comprising a polymer of the group consisting ofacrylonitrile-butadiene-styrene terpolymer, hydrocarbon polymers andhalogen-containing follows: polymers, stabilized with phosphites of theformula increase in No. of Repeating Moles of Moles of Moles of Mole ofR,OH Units Formula (6) Formula (3) R OH Split For Add. Unit 2 2 l 2 3 32 4 2 4 4 3 6 2 5 5 4 8 2 6 6 5 l0 2 7 7 6 l2 2 8 8 7 l4 2 9 9 8 l6 2However, if one end group is to be reacted, the moles of Formula (3)must be increased by l or if both end groups are to be reacted, themoles of Formula (3) must be increased by 2. Of course, the moles of ROH split out will also increase by l or 2, respectively. ln other words,the number of moles of R Ol-l split out will be 2 times the number ofmoles of Formula (3) used in forming the repeating units plus 1additional mole of R OH for each end group reacted. An analogoussituation exists for each of the products of the invention.

tcwhatisclaimed m,

and

and the position isomers thereof and where Q is 55 OCH: R

n is 0 to and R is WW R is aryl, alkyl, haloaryl, haloalkyl, alkaryl,alkenyl and haloalkenyl, and R is a hydrogenated dihydric phenol moiety.

9. A composition according to claim 8 wherein the polymer is a vinylchloride resin.

10. A composition according to claim 9 wherein the 5 vinyl chlorideresin is a rigid vinyl chloride resin having not over 10% plasticizer.

15 16 11. A composition according to claim 8 wherein the polymer isselected from the group consisting of diolepolymer a monoolefin polymerfin homopolymers, butadiene-styrene copolymer and 12. A compositionaccording to claim 11 wherein the polymer is polypropylene.

13. A composition according to claim 8 wherein the 5acrylonitrile-butadiene-styrene terpolymer.

2. A composition according to claim 1 where n of formula (2) is equal to2.
 3. A composition according to claim 1 wherein the polymer is a vinylchloride resin.
 4. A composition according to claim 3 wherein the vinylchloride resin is a rigid vinyl chloride resin having not over 10%plasticizer.
 5. A composition according to claim 1 wherein the polymeris a monoolefin polymer.
 6. A composition according to claim 5 whereinthe polymer iS polypropylene.
 7. A composition according to claim 1wherein the polymer is selected from the group consisting of diolefinhomopolymers, butadiene-styrene copolymer andacrylonitrile-butadiene-styrene terpolymer.
 8. A composition comprisinga polymer of the group consisting of acrylonitrile-butadiene-styreneterpolymer, hydrocarbon polymers and halogen-containing polymers,stabilized with phosphites of the formula
 9. A composition according toclaim 8 wherein the polymer is a vinyl chloride resin.
 10. A compositionaccording to claim 9 wherein the vinyl chloride resin is a rigid vinylchloride resin having not over 10% plasticizer.
 11. A compositionaccording to claim 8 wherein the polymer is a monoolefin polymer.
 12. Acomposition according to claim 11 wherein the polymer is polypropylene.13. A composition according to claim 8 wherein the polymer is selectedfrom the group consisting of diolefin homopolymers, butadiene-styrenecopolymer and acrylonitrile-butadiene-styrene terpolymer.